(+)-(3aR,6aS,6bS)-6a-(3,4-dimethoxyphenyl)-4,4-(2,2-dimethylpropylenedioxy)perhydropyrrolo(3,2,1-ij)benzoxazine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (+)-(3aR,6aS,6bS)-6a-(3,4-dimethoxyphenyl)-4,4-(2,2-dimethylpropylenedioxy)perhydropyrrolo(3,2,1-ij)benzoxazine
• 英文别名: (4'S,8'R,12'S)-4'-(3,4-dimethoxyphenyl)-5,5-dimethylspiro[1,3-dioxane-2,7'-10-oxa-1-azatricyclo[6.3.1.04,12]dodecane]
• 化学式: C₂₃H₃₃NO₅
• 分子量: 403.519
• InChiKey: ACUASSCPKHSBCV-XJABCFGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  49.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1,5-二溴-3-戊酮 在 镍 2,6-二叔丁基-4-甲基苯酚 、 氢气 、 双氧水 、 三甲基铝 、 对甲苯磺酸 、 sodium iodide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 丙酮 、 甲苯 、 苯 为溶剂， -15.0~25.0 ℃ 、2.07 MPa 条件下， 反应 138.5h， 生成 (+)-(3aR,6aS,6bS)-6a-(3,4-dimethoxyphenyl)-4,4-(2,2-dimethylpropylenedioxy)perhydropyrrolo(3,2,1-ij)benzoxazine
  参考文献：
  名称：

  Asymmetric Construction of a Quaternary Carbon Center by Tandem [4 + 2]/[3 + 2] Cycloaddition of a Nitroalkene. The Total Synthesis of (−)-Mesembrine

  摘要：

  An efficient, total synthesis of the Sceletium alkaloid (-)-mesembrine is accomplished in seven steps and 19% yield from a functionalized nitroalkene (itself prepared in six steps and 34% yield from ethyl 3-bromopropionate). The construction of the octahydroindole framework of mesembrine features a tandem inter [4 + 2]/intra [3 + 2] cycloaddition of a 2,2-disubstituted 1-nitroalkene and a chiral vinyl ether derived from (1R,2S)-2-(l-methyl-l-phenylethyl)cyclo as the central strategic element. The two stereogenic centers of the natural product, which include a benzylic, quaternary center, were established in 26/1 selectivity in the tandem process.

  DOI：

  10.1021/jo970079z

文献信息

• Asymmetric Construction of a Quaternary Carbon Center by Tandem [4 + 2]/[3 + 2] Cycloaddition of a Nitroalkene. The Total Synthesis of (−)-Mesembrine
  作者：Scott E. Denmark、Lawrence R. Marcin

  DOI：10.1021/jo970079z

  日期：1997.3.1

  An efficient, total synthesis of the Sceletium alkaloid (-)-mesembrine is accomplished in seven steps and 19% yield from a functionalized nitroalkene (itself prepared in six steps and 34% yield from ethyl 3-bromopropionate). The construction of the octahydroindole framework of mesembrine features a tandem inter [4 + 2]/intra [3 + 2] cycloaddition of a 2,2-disubstituted 1-nitroalkene and a chiral vinyl ether derived from (1R,2S)-2-(l-methyl-l-phenylethyl)cyclo as the central strategic element. The two stereogenic centers of the natural product, which include a benzylic, quaternary center, were established in 26/1 selectivity in the tandem process.